Redenti E, Delcanale M, Amari G, Ventura P, Bacchi A, Pelizzi G
Chemical and Biopharmaceutical Department, Chiesi Farmaceutici S.p.A., Parma, Italy.
J Pharm Sci. 1995 Sep;84(9):1126-33. doi: 10.1002/jps.2600840917.
The solid state structures of the (-)-n-heptylcarbamate of geneseroline and its hydrochloride salt were determined by single crystal X-ray diffraction analysis. Both compounds gave crystals belonging to the orthorombic P2(1)2(1)2(1) space group with a = 27.597(7) A, b = 8.899(2) A, c = 9.290(2) A, V = 2281.5(9) A3, Z = 4, and R = 0.0682 for the base and a = 11.300(1) A, b = 8.3485(5) A, c = 24.141(2) A, V = 2277.3(3) A3, Z = 4, and R = 0.0482 for the salt. X-ray and 1H NMR analysis revealed that the base is a 1,2-oxazine derivative. The six-membered ring adopts a 4C1 chair conformation in the solid-state, whereas, in CDCl3 solution, it exists as a mixture of two possible chair conformers, 4C1 and 1C4, with the N-methyl group in the equatorial position (ratio approximately 75:25). The salt is an N-oxide derivative; the five-membered ring adopts different envelope conformations in the solid-state and in CDCl3 solution, suggesting a certain flexibility. In more polar solvents, the salt partially undergoes fast inversion at the tetrahedral nitrogen, giving rise to the corresponding epimer.
通过单晶X射线衍射分析确定了吉尼色林的（-）-正庚基氨基甲酸酯及其盐酸盐的固态结构。两种化合物的晶体均属于正交晶系P2(1)2(1)2(1)空间群，碱的晶胞参数为a = 27.597(7) Å，b = 8.899(2) Å，c = 9.290(2) Å，V = 2281.5(9) Å3，Z = 4，R = 0.0682；盐的晶胞参数为a = 11.300(1) Å，b = 8.3485(5) Å，c = 24.141(2) Å，V = 2277.3(3) Å3，Z = 4，R = 0.0482。X射线和1H NMR分析表明，该碱是一种1,2-恶嗪衍生物。六元环在固态时采用4C1椅式构象，而在CDCl3溶液中，它以两种可能的椅式构象4C1和1C4的混合物形式存在，N-甲基处于赤道位置（比例约为75:25）。该盐是一种N-氧化物衍生物；五元环在固态和CDCl3溶液中采用不同的信封式构象，表明具有一定的灵活性。在极性更强的溶剂中，该盐在四面体氮处部分发生快速翻转，产生相应的差向异构体。
